Merocyaninic dyes and their use in silver halides photographic emulsions containing the same

ABSTRACT

Merocyanine dyes comprising a heterocyclic nitrogenous nucleus and a heterocyclic ketomethylene nucleus, and silver halide emulsions containing such dyes.

Sores karenr [191 Berewn et a1.

[ Sept. 17, 1974 1 1 MEROCYANINIC DYES AND THEIR USE IN SlILVIERll-IALIDES IPHOTOGRAPHIC EMULSlONS CONTAINING THE SAME [75] Inventors:Paolo Beretta, Ferrania; Luigi Magnani, Carcare, both of Italy [73]Assignee: Minnesota Mining and Manufacturing Company, St. Paul, Minn.

22 Filed: Mar.8,1972

211 Appl.No.:232,724

[30] Foreign Application Priority Data Mar. 9, 1971 Italy 48919/71 [52]US. Cl 96/127, 96/139, 96/141, 260/2401, 260/240.4

[51] on. C1 G03C 11/11) Primary Examiner-J. Travis Brown Attorney,Agent, or Firm-Alexander, Sell, Steldt & DeLaHunt [57] ABSTRACTMerocyanine dyes comprising a heterocyclic nitrogenous nucleus and aheterocyclic ketomethylene nucleus, and silver halide emulsionscontaining such dyes.

5 Claims, 8 Drawing Figures PATENIEU 3. 836.3 70

SHEEI 1 nr 3 MEROCYANINIC DYES AND THEIR USE IN SILVER HALIDESPHOTOGRAPHIC EMULSIONS CONTAINING THE SAME The present invention relatesto merocyaninic dyes and to silver halides emulsions containing the sameand to photographic elements containing such dyes.

Silver halides, by themselves, are substantially insensitive to thevisible radiations with the exception of those having a lower wavelength. The sensitivity of the silver halides emulsions has beenextended to higher wave lengths by the introduction into them of variousdyeing sensitizers such as those of the merocyaninic class. These dyesare now of common use in the black and white photographic emulsions andin the colored photographic emulsions. For example, a usefulphotographic element for colored photography may contain layers ofsilver halides emulsion which have been sensitized to the red, green andblue light. The dyeing sensitizers used in the above photography mustexhibit, according to what hereinabove said, the sensitizationcharacteristics required and moreover they must be completely removablefrom the photographic elements during the processing so as to impart theleast residual coloration possible to the final colored image.

A summary of the technology of the dyeing sensitizers and examples ofvarious dyeing sensitizers may be found in Mees and James, The Theory ofthe Photographic Process, Third Edition, The McMillan Company, New York,1966, Chapter 1 1. For the desensitizers re same Chapter 11 and 8 ande.g. British Patent l,186,713.

In brief the present invention relates to merocyaninic dyes comprisingon one side a heterocyclic, nitrogeneous nucleus and on the other one ofa heterocyclic ketomethylenic nucleus.

These merocyaninic dyes are characterized by the ketomethylenic groupcontaining at least a nitrogen atom, carrying, as a substituent, afurfurylor a tetrahydrofurfuryl group. The invention relates moreover tophotographic silver halides emulsions containing such dyes, assensitizers and desensitizers, and to photographic elements preparedwith them.

In its preferred realization, the presentinvention refers tomerocyaninic dyes representatable by the following formula:

In the hereinabove formula,

R represents a substituted and a non substituted alkyl having from oneto eight carbon atoms such as for ex- LII ample methyl, ethyl,hydroxyethyl, sulphoethyl, car- Z represents the non metallic atomsrequired to complete a heterocyclic nucleus.

Q represents the non metallic atoms necessary to completea heterocyclicnucleus comprising at least a nitrogen atom carrying, as a substituent,a furfuryl or a tetrahydrofurfuryl group.

nis l or2anddis 1,2or3.

Examples of heterocyclic rings which are completed by the non metallicatoms represented by Z in the hereinabove formula (1) are those of thethiazole series (thiazole, 4-methyl-thiazole, 4-phenylthiazole, 5-methyl-thiazole, S-phenyl-thiazole, 4,5-dimethylthiazole,4,5-diphenyl-thiazole); those of the benzothiazole series(benzothiazole, 4-chlorobenzothiazole, 5- chloro-benzothiazole,6-chloro-benzothiazole, 7- chloro-benzothiazole, 4-nitro-benzothiazole,S-nitrobenzothiazole, 6-nitro-benzothiazole,5-chloro-6-nitrobenzothiazole, 5-bromo-o-nitrobenzothiazole,4-methyl-benzothiazole, S-methyl-benzothiazole, 6- methylbenzothiazole,S-bromo-lbenzothiazole, 6- bromo-benzothiazole, 4-phenylbenzothiazole,S-phenyl-benzothiazole, 4-methoxy-benzothiazole, 5-methoxybenzothiazole, 6-methoxy-benzothiazole, 5-

methyl-6-methoxy-benzothiazole, 5-iodobenzothiazole,6-iodo-benzothiazole, 4-ethoxybenzothiazole, 5 -ethoxy-benzothiazole,4,5 ,6, 7-

tetrahydro-benzothiazole, 5,'6-hydroxymethylenbenzothiazole,S-hydroxy-benzothiazole, o-hydroxybenzothiazole,5,6-dimethyl-benzothiazole, 5,6-dimethoxy-benzothiazole); those of thenaphthothiazole series l,2-d]-naphthothiazole, [2, l -d]-naphthothiazole, 5-methoxy-[ l ,2-d]-naphthothiazole, 5-ethoxy-[ 1,2-d]-naphthothiazole, 8-methoxy-[2, l -d]- naphthothiazole,7-methoxy-[2,1-d]-naphthothiazole); those of the oxazole series (4-methyl-oxazole, 5- methyl'oxazole, 4-phenyl-oxazole,4,5-diphenyloxazole, 4-ethyl-oxazole, 4,5-dimethyloxazole, 5-phenyl-oxazole; those of the benzoxazole series (5- chloro-benzoxazole,5-methyl-benzoxazole, S-phenylbenzoxazole, 6-methyl-benzoxazole,5,6-dimethylbenzoxazole, 4,6-dimethyl-benzoxazole, S-metoxybenzoxazole,S-hydroxy-benzoxazole, o-hydroxybenzoxazole, 4-nitro-benzoxazole,S-nitrobenzoxazole, 6-nitro-benzoxazole, 5-chloro-6-nitrobenzoxazole,5-bromo-6-nitro-benzoxazole; those of the naphthoxazole series([2,l-d]-naphthoxazole, [1,2- dl-naphthoxazole); those of the selenazoleseries (4- methyl-selenazole, 4-phenyl-selenazole); those of thebenzoselenazole series (benzoselenazole, S-chlorobenzoselenazole,5-metoxy-henzoselenazole, 5- hydroxy-benzoselenazole,fi-metoxy-benzoselenazole, 5,6-dimetoxy-benzoselenazole,4-nitrobenzoselenazole, S-nitro-benzoselenazole, 6-nitrobenzoselenazole,5-chloro-6-nitro-benzoselenazole, 5- bromo-6-nitro-benzoselenazole;those of the naphthoselenazole l ,2-d]-naphthoselenazole, [2, l -d]-naphthoselenazole); those of the thiazoline series (thiazoline,4-methyl-thiazoline, 4-hydroxymethylthiazoline,4,4-bis-hydroxymethyl-thiazoline, 4- acetoxymethyl-4-methyl-thiazoline,4,4-bis-acetoxymethyl-thiazoline); those of the oxazoline series(oxazoline, 4-hydroxymethyl-4-methyl-oxazoline,4,4-bisacetoxymethyl-oxazoline); those of the selenazoline series, thoseof the Z-quinoline series (quinoline, 3- methyl-quinoline,Smethyl-quinoIine, 7-methylquinoline, 3-methyl-quinoline,6-chloro-quinoline, 8- chloro-quinoline, o-methoxy-quinoline,6-etoxyquinoline, 6-hydroxy-quinoline, 8-hydroxy-quinoline); those of4-quinoline series (quinoline, 6-methoxyquinoline, 7-metoxy-quinoline,8-methyl-quinoline); those of the l-isoquinoline series (isoquinoline,3,4- diisoquinoline); those of the 3-isoquinoline series; those of the3,3-dialkyl-indolenine series (3,3- dimethyl-indolenine,3,3,S-trimethyl-indolenine, 3,3,7- trimethyl-indolenine); those of the2-pyridine series (such as for example 2-pyridine, S-methyl-Z-pyridine,etc); those of the 4-pyridine series (4-pyridine, 3-methyl-4-pyridine,etc. those of the imidazole series (for example imidazole,l-alkyl-imidazole, 1-alkyl-4- phenyl-imidazole,l-alkyl-4,5-dimethyl-imidazole, ctc.); those of the henzimidazole series(for example bcnzimidazolc, l-alkyl-bcnzimidazolc, l-alkyl-5,6-dichloro-benzimidazole, l-phenyl-benzimidazole,lhydroxyethyl,5,6-dichloro-benzimidazole, l-ethyl-S-chloro-benzimidazole, l-acetoxyethyl-S ,6-dichlorobenzimidazole,l-ethyl-5-chloro-6-aminobenzimidazole,l-ethyl-5-chloro-6-bromobenzimidazole, l-ethyl-5-acetyl-benzimidazole,etc.

Examples of nuclei which are completed by atoms represented by Q in thehereinabove formula (1) are the nucleus of the thiazole, for example2,4-thiazoledione, 4-thiazolidone, 2-thio-2,4-thiazole-dione (roda'nine); nuclei of the oxazolone type, for example 2-thio-2,4-oxazole-dione and 2-imino-2,4 oxazole-dione (pseudo-hydantoin);nuclei of the imidazolone type, such as the 2,4-imidazole-dione(hydantoin, for example 2-thio-2,4-imidazolo-dione (2-thio-hydantoin);nuclei of the pyrazolone type, oxindole (2,3- dihydroketoindole),2,4,6-triketohexahydropyrimidine (barbituric or thiobarbituric acid);nuclei of the 3,4-dihydro-quinoline, 3,4-dihydroquinoxazolone,l,4-rnorpholine-3-one and 2H-l,4-benzothiazine-3-one.

The merocyaninic dyes of the present invention represented by thegeneral formula l wherein d is equal to I, can be prepared by reactingan ammonium salt chosen among those known to the skilled in the art,represented by the formula:

wherein R and Z have the hereinabove reported values;

R represents an alkyl group (such as for example methyl, ethyl, etc.) oran aryl group (such as for example phenyl, o-, m-, p-tolyl, etc.);

X represents an acid anion such as chloride, bromide, iodide,thiocyanate, sulfamate, methylsulfate, ethylsulfate, perchlorate,benzensulfonate, p-toluenesulfonate, etc. with a compound chosen amongthose represented by the following formula:

ma -(i=0 where Q has the hereinabove reported meaning.

The compounds (3) not known before the present invention, as theycontain the furfurylor the tetrahydrofurfuryl substituent, can beprepared in a way known to the skilled in the art, as it results fromthe hereinafter following description and examples.

The dyes according to the invention represented by the general formula lwhere d 2, 3 can be prepared by condensing a compound of the generalformula (3) with a compound chosen among those known to the skilled inthe art, represented by the general formula:

wherein R, Z and n have the meanings hereinabove reported.

Another process usefully employed in the synthesis of the merocyaninicdyes of the general formula (1) with d 2 and L equal to substitutedmethinic group as hereinabove reported, consists of the condensation ofa compound of the general formula (3) with a compound chosen among theclass known to the skilled in the art, represented by the formula:

where R, R,, X, Z and n have the meaning hereinabove reported and R isequivalent to monovalent alkyl group such as methyl, ethyl, etc.

Another method to prepare the merocyaninic dyes of the general formula(1), where d 2 and L is equal to non substituted methinic group consistsof reacting a quaternary salt belonging to the class of the compoundsknown to the skilled in the art, represented by the following formula:

where R, X, Z, n have the hereinabove cited meanings, with a compoundbelonging to the class represented by the following formula:

where Q, R R have the hereinabove cited meanings.

The compounds of the formula (8), not know before the present invention,as they contain the furfurylor the tetrahydrofurfuryl substituent, canbe prepared in a way known to the skilled in the art, from compound offormula (3), as it results also from the examples following hereinafter.

The condensations of which hereinabove, can be ad vantageously performedby heating the reacting mixture at temperatures ranging between roomtempera-' where R, L, Z, n and d have the meanings hereinabove reportedand where at least one among the substituents R and R is a furfurylortetrahydrofurfuryl group, while the other one is an alkyl group (forexample methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl, nheptyl,benzyl (phenylmethylene), allyl, cyclo-penty], cyclo-hexyl, etc.; asubstituted alkyl group such as car- 'boxyethyl, carboxymethyl,sulfo-propyl, dialkylaminoalkyl, etc.; an aryl group such as phenyl, 0-,m-, ptolyl.

The compounds (9) are prepared according to the above indicated generalmethods, from compounds not known before the present invention, havingthe formula:

where R and R have the hereinabove reported mean- 6 ings, obtained in aknown way, for example according to Wheeler and Al, J.A.C.S. (1911), 45,456-474, and from compounds not known before the present invention,having the formula obtained in a way known to the skilled in the artfrom compounds having the formula (10) as it results from the followingexamples.

Among the compounds represented by formula (1), particularly useful arealso the merocyanines represented by the following formula:

Ike

where R, L, Z, n, d, have the hereinabove said meanings W is equal to Sand O and R represents a furfuryl or tetrahydrofurfuryl radical.

The compounds (12) are prepared according to the most general methodshereinabove reported, from compounds not known before the presentinvention,

having the formula:

(12) bis CH;W

where W and R have the hereinabove reported meanings, obtained in a wayknown to the skilled in the art, for example according to Holberg and Alin K. Prakt, Chemie, 81 (1910) 451 and Andreasch and Zizsser inmonatschr. fur Chemie 24 (1903) 504 and 25 (1904) 167 and according toA. Ahlquist in Journ. Prakt. Chemie [2], 84 (1911), 662-675, and fromcompounds, not known before the present invention, having the formula:

obtained in a way known to the skilled in the art from compound havingthe formula 12 bis) as it results also from the following examples.

The sensitizers of the present invention introduced into the silverhalides photographic emulsions have the advantage of imparting to themand to the photographic element containing them a more extended spectralsensitization (and therefore a greater sensitivity) and of notpresenting any residual coloring.

The present invention will be more easily understood, by referring tothe following illustrative examples.

Example 1 Tetrahydrofurfuryl-isothiocyanate CH;-CH:

H2 I'L-GHPN C S o 24 g of NaOH drops were dissolved in 120 cc of waterand to this solution 52.5 g of tetrahydrofurfurylamine were added. Thestirred mixture was brought by cooling to +4C and then 60.3 g of carbonsulfide were added in small portions. The temperature was maintainedbelow 10C during the whole period of the addition. The mixture was leftunder stirring for 7 hours and then allowed to stand at rest overnight.A solution of 228 g of lead acetate in 240 cc of water was poured intothe reaction mixture under stirring at room temperature and thesemisolid black mass obtained was diluted with 200 cc of water andfurtherly stirred for 2 hours. The mixture was steam distilled until 3liters of distillate were obtained; the distillate was then'extractedwith ethyl ether. The ethereal solution was dried with Na SO andevaporated to dryness. A dark dense oil (34 g) was obtained, which wasdistilled under vacuum. The fraction distilled at ll-ll5C/27 mm Hg wascollected.

The yield was 16 g.

Example 2 furfuryl-senfol This compound has been prepared similarly tothe preceeding one by using 50 g of furfurylamine, 22.8 g of NaOH in l14 cc of water, 60.3 g of CS and a solu tion of 240 g of lead acetate in600 cc of water. At the end a dark dense oil was obtained which wasimmediately used without further purification, since it decomposed veryeasily (even if stored under vacuum).

Example 3 l-methyl-3-tetrahydro-furfuryl-Z-thio-hydantoin Centesimalanalysis Found: C% 50.78; H% 6.82; N% 12.87

14.75 Calculated: C% 50.51; H% 6.59; N% 13.09

Example 4 l-carboxymethyl-3-tetrahydrofurfuryl-2- thiohydantoin 37.6 gof the iminoacetic acid diethyl ester were introduced in a flasksupplied with reflux and dropper. From the latter 28.5 g oftetrahydrofurfuryl-senfol (example 1) were allowed to drop in and thenthe mixture was boiled for 10 minutes. The reaction mixture was pouredin a vessel containing 200 cc of cold water; an oil was separated whichwas extracted with ethyl ether. The ethereal solution was treated withbone black, dried with Na SO and evaporated ultil dryness.

The yield was 55.4 g and thus it was obtained thelcarboxyethoxymethyl-3-(tetrahydrofurfuryl)-2- thiohydantoin. Thisproduct was treated with 186 cc of a 10 percent sodium hydroxidesolution, heating to boiling for 10 and thus obtaining a completesolution. After acidification with HCl and cooling, the mixture wasextracted with ethyl ether. The solution was dried with Na SO andevaporated.

A dark oil (9.5 g) was obtained, which was used immediately for thesynthesis of the dyes without further purification.

Example 5 N-tetrahydrofurfuryl-rodanine 18 g oftetrahydrofurfuryl-senfol, 32 g of absolute alcohol and 16 g ofthioglycolic acid were introduced into a 250 cc flask and placed on anoil bath at l 10C. After 1 hour, 2 cc of acetic anhydride were added andthe heating was continued for 24 hours. A yellow solution was obtainedwhich was concentrated under vacuum until the formation of a solid whichwas filtered on a buckner.

The yield was 10.7 g of dried product. The raw product was crystallizedfrom 425 cc of ligroin and 9.4 g of pure product having a M.P. 88-89Cwas obtained.

Centesimal analysis Found: Cal cu lated:

Example 6 Acetamidofurfurylamine hydrochloride g of furfurylamine, 486.4g of chloroacetamide and 1600 cc of absolute alcohol, were heated at5050C on a steam bath for 2 hours and then at reflux for 4 hours. Themixture was cooled and allowed to stand. A brown solid was separated andwas filtered on a buckner. The solid was mashed with acetone severaltimes until it became white; it was collected on a buckner and washedwith ethyl ether. The flaky white product obtained was dried and gave ayield of 186 g M.P. l80.5 l8l.5C.

Example 7 1-furfuryl-3-(y-dimethylaminopropyl )-2- thiohydantoin In arefluxing flask placed in an oil bath at 100C, 52.5 g ofacetamido-furfurylamine hydrochloride, 100 cc of methyl alcohol and 39 gof -di-methylaminopropyl-senfol were introduced. A vivacious reactionoccurred which was quenched by immerging the flask into a bath of waterand ice. 200 cc more of methyl alcohol were added and to the dark resulting mixture 16.6 g of potassium hydroxide dissolved in 110 cc ofwater were added and the mixture was boiled for 3 hours, making sureonce in a while that the pH remained alkaline. When the heat wasterrnined, to the likewarm solution 137 cc of concentrated HCl wereadded in small portions. When the addition was terminated, the mixturewas brought to ebullition again for 3 hours making sure that the pHremained acid; then it was allowed to stand overnight. A solid wasseparated and was eliminated by gravity filtering. The mixture wasevaporated under vacuum until a solid remained. It was diluted withwater, alkalized to pH 9 with percent sodium carbonate, extracted withethyl ether and finally the ethereal soluion was dried. The mixture washeated with bone black and was evaporated. A dark oil remained, theyield of which was 59.5 g. The product, which was difficult to purifywas immediately used for the dye synthesis.

Example 8 N-furfuryl-rodanine The reaction was performed similarly tothat one of Example 5. The amounts used were 40 g of furfurylsenfol, 73cc of ethyl alcohol, 4.5 cc of acetic anhydride and 36 g of thioglycolicacid. The obtained yield was 7.2 g of oil which was distilled underreduced pres sure. B.P. ll6l20C/l mm Hg.

Example 9 l-furfuryl-3-propyl-thiohydantoin 52.5 g ofacetamido-furfurylamine hydrochloride, 300 cc of methyl alcohol, 27.8 gof propyl-senfol and 16.6 g of KOH dissolved in 110 cc of water, weremixed in a l l flask. The mixture was boiled for 3 hours then I37 cc ofconcentrated HCl were added after cooling the flask with water and ice.The mixture was then boiled for half an hour and then 200 cc of solventwere distilled off. The mixture was diluted with 200 cc of water and wasextracted with ethyl ether, drying the ethereal solution with Na SOAfter evaporation of the ether, 53 g of a dark yellow oil remained whichwas distilled under vacuum collecting the fraction distilled at168l70C/l mm Hg. The yield was 45.5 g ofa slightly yellow oil.

Centesimal analysis Calculated: Found:

Example 10 N-furfurylglycine ethyl ester 30 g of furfurylamine, togetherwith cc of absolute ethyl alcohol, were introduced in a flask and from areflux 54 g of ethyl bromo-acetate were added. A dark solution wasobtained and 32 g of triethylamina were added to it. A white solidseparated. The mixture was brought to ebullition and was allowed toreact for 15 hours while the solid went completely into solution. Bycooling and standing a solid tri-ethylamine hydrobromide separated,which was separated from the solution by filtration on a buckner. Tothe: solution was added more ethyl ether to complete the triethylaminehydrobromide precipitation. The ethereal solution was concentrated underreduced pressure and the remained dark oil was diluted under vacuumcollecting the fraction having a HP. l60l 70C/2 mm Hg. The obtainedyield was 33.6 g.

Example 1 l l-furfuryl-3-carboxymethyl-2-thiohydantoin oH,--N-orn-o ofthis product were boiled for minutes with 82 cc of a 10 percent sodiumhydroxide. The dark yellow solution obtained was cooled and acidifiedwith HCI. Then it was extracted with ether, the ethereal solution wasdried with anhydrous sodium sulfate and then was evaporated undervacuum. The residual yellow oil by standing a few days in thedessiccator, solidified and was crystallized from ethyl alcohol. Yield23 g M.P. l25126C.

Centesimal analysis Calculated: Found:

C% 47.24; H% 3.94; N C% 47.36; H% 4.09; N

Example 12 l-tetrahydrofurfuryl-3-ethyl-2thiohydantoin JaHr 9.8 g ofN-tetrahydrofurfuryl-glycine-ethyl ether (Example 11) and 4.45 g ofethylsenfol were heated at 150C for 36 hours. The obtained dense liquidwas distilled under vacuum and a yellow oil having a B.P. 168l 72C/ 1 2mm Hg was obtained. The yield was 7.1

Example 13 l-carboxymethyl-3-tetrahydrofurfuryl-2- thiohydantoin N am HCH: O

- were dissolved in 186 cc of 10 percent sodium hydroxide by boiling for5 minutes. The solution'was poured into a beaker containing 200 cc ofwater and while cooling in a bath of water and ice was acidified withconcentrated HCl and was extracted with ethyl ether. The etherealsolution dried with anhydrous sodium sulfate was evaporated obtaining anoil which solidified after some days. The product was used as such forthe synthesis of the dyes.

Example 14 N-furfuryl-2-thio-oxazolidone 26.1 g of furfuryl-amine and asolution consisting of 21.19 g of potassium hydroxyde dissolved in 81.8cc of water were mixed in a keller. Under fast stirring 57 g ofacetamido-carbodithioloneglycolic acid (prepared according to what hasbeen reported in J. Prakt. Chem./2/99 (1919) p. 45 and following), wereadded in small portions. The mixture was allowed to stand overnight, wasdiluted with 271 cc of water and was stirred again for 2 hours then wasacidified with HCl. A separated oil was extracted with ethyl and theethereal solution was dried with anhydrous sodium sulfate. The solutionwas filtered by gravity and the solvent was evaporated. A yellow oilremained giving a yield of 63 g. It was distilled under reduced pressureand the fraction distilled at 168170C llmm Hg was collected; its weighttotaled 38.6 g. after a little while it solidified in a crystalline masswhich was crystallized from ethyl alcohol. 26.5 g of shining whitescales were obtained, having M.P. 68.569C. The compound was found tocomply with the formula:

l... 1 C O Centesimal analysis Calculated: 7.1 1 Found: 7.12

Example 15: N-tetrahydrofurfuryl-2-thio-oxazolidone.

CH2O

N (EH2 It was prepared analogously to Example 14, by using 27.1 g oftetrahydrofurfuryl-amine, 21.19 g of potassium hydroxide, 81.8 cc ofwater and 37.5 g of acetamido-carbodithiolone-glycolic acid. Byevaporation of the ethereal solution 37 g of reddish oil were obtained;the oil was distilled under vacuum and the fraction distilled at ll82C/1 mm Hg was collected. The yield was 20.15 g.

Centesimal analysis Calculated: Found:

Example 16 -acetanilido methylene-3-furfuryl-2-thiooxazolidone.

9.85 g of N-furfuryl-2-thio-oxazolidone, 9.80 g of diphenyl-formamidineand 3 cc of kerosene were reacted for 2 and a half hours at 120C. An oilseparated and solidified after standing overnight. The yield of the pureproduct, having MP. 165-l67C was 5.7 g. 4.7 g of this product(5-anilino-methylene-3-furfuryl-2- thio-oxazolidone) were refluxed withcc of acetic anhydride and 3 cc of trimethylamine for an hour. Thesolution was poured into a beaker containing 250 cc of water. Theobtained solidified oil was crystallized from ethyl alcohol. A yield of4 g of yellow needless having M.P. l37138C was obtained.

Example 175-acetanilido-methylene-3-tetrahydrofurfuryl-2-thiooxazolidone It wasprepared analogously to the intermediate 16, using theN-tetrahydrofurfuryl-Z-thio-oxazolidone instead of theN-furfuryl-2-thio-oxazolidone. At the end of the operation, 3,5 g ofcrystallized product having MP. l74 -175C were obtained.

Example 18 5 -acetanilido methylene-1-furfuryl-3 -propyl-2-thiohydantoinThe reaction was analogous to that of Example 16.15 g ofl-furfuryl-3-propyl-2-thiohydantoin, 12.3 g of diphenyl-formamidine and45 cc of kerosene were used. The5-anilino-methylene-l-furfuryl-3-propyl-2- thiohydantoin obtained (8.5 gM.P. l24-5C) was boiled with acetic anydride and triethylamine. Theyield of the crystallized product was 3.5 g, MP. l67-9C.

Example 19 5-( 3 -ethyl-thioazolidine-Z-ylidene-ethylidene )-3-tetrahydroiu rfuryl'rodanine 1,39 g of tetrahydro-furfuryl-rodanine, 2 gof 2-(wacetanilido-vinyl)thioazoline-iodo-ethylate, 15 cc of ethylalcohol and 1 cc of triethylamine, were boiled for 20 minutes obtainingan orange solution. The solution was cooled and precipitated with water.A fluid pitch separated and it hardened after standing. It was boiledtwice with water and crystallized from ethyl alcohol. Shining violaceousscales were obtained having M.P. 148C.

()t max of absorption is ethanol: 485 nm) Centesimal analysis Calculated5 Found:

Example 20 5-( 3-methylbenzoxaline-2-ylidene-ethylene-)-3-tetrahydrofurfuryl-rodanine as t. 5H3 EH2 2.78 g ofN-tetrahydrofurfuryl-rodanine, 4.2 g of2-(wacetanilidovinyl)benzoxazole-iodo-methylate, cc of ethylic alcoholand 3 cc of triethylamine, were boiled for 20 minutes, obtaining anorange solution. By cooling it separated the dye which was crystallizedfrom a mixture of pyridine and ethyl alcohol in the ratio 2:1.

Red shining crystals having M.P. 212-215C were obtained. (kmax ofabsorption in ethanol: 41-93 nm) Centesimal analysis Calculated:C%=57.30; H%=4.85; N=7.49; S=l7.l5 Found: C%=57.76; H%=5.03; N%=7.38;S%=l7.l0

Example 21 CH: \N/ (in.

(A max of absorption in ethanol: 456 nm) 15 Example 22 5-( l:2-dihydro-l-methyl-6-metoxiquinoline-2- ylidene)-3-tetrahydro-furfuryl-2-thio-oxazolidone N (EH2 Hr Hz 2 g ofN-tetrahydrofurfuryl-Z-thio-oxazolidone, 3.28 g of2-ethylmercapto-6-methoxyquinoline-bromoethylate, 25 cc of ethylalcohol, 0.5 cc of triethylamine, were boiled for 15 minutes. The orangedye separated out in the hot and was filtered and washed with ethylalcohol and ethyl ether. The product was boiled with water andcrystallized from ethyl alcohol and needlelike crystals having goldenreflexes were obtained. The yield was 1.7 g, the M.P. 1945C.

()t max of absorption in ethanol: 458-486 nm):

Centesimal analysis Calculated: Found:

Example 23 5-(1-,8-acetoxyethyl-3-carboxyethyl-5.6-dichlorobenzimidazoline-Z-ylidene-ethylidene)-3- tetrahydrofurfuryl-2-thio-oxazolidone pmcmo O CH3 N 01 C=CHCH=:;- Z01 N Hz-CHz-OQOH 5 Hz-( H2 0.86 g of 5-acetanilido-methylene-3-tetrahydrofurfuryl-2-thioxazolidone, 1.1 g of l-B-acetoxy-ethyl-Z-methyl-S.6-dichlorobenzimidazole-3- carboxyethylbromide, 30 cc of butyl alcohol and 3 cc of triethylamine were boiledfor 2 hours. The mixture was concentrated under vacuum and was boiled inwater; finally it was crystallized from ethyl alcohol. Red microcrystalshaving M.P. 209-2l0C were obtained.

(A max of absorption in ethanol 498 nm) Example 24 5-(l-B-acctoxycthyl-3-ethyl-5.6-dichlorobenzimidazoline-Z-ylideneethyldene)-3- tetrahydrofurfuryl-2-thio-oxazolidonetetrahydrofurfuryl-2-thiooxazolidone, 1.1 g of l-B-acetoxyethyl-Z-methyl-S.6-dichlorobenzimidazoleiodo-ethylate, 30 cc ofbutyl alcohol and 3 cc of trimethylamine were boiled for 2 hours. Themixture was concentrated under vacuum. The solid product separated wasboiled with water, crystallized from ethyl alcohol and allowed to standat room temperature. Violet crystals M.P. -181C were obtained.

(A max of absorption in ethanol: 497 nm).

Example 25 5-[-,8-acetoxyethyl-3-carboxyethyl-5.6dichlorobenzimidazoline-2-ylidene]-3-furfuryl-2-thiooxazolidoneICHQCHQOOOCH: N 01 C=CHCH=C-E Cl N e N HQCHZCOOH 5 0.8 g of5-acetanilido-methylene-3-furfuryl-2-thiooxazolidone, 1.1 g of1-(B-acetoxyethyl)2-methyl-5.6- dichloro-benzimidazole-3-carboxyethylbromide, 15 cc of butyl alcohol, 1.5 ccof triethylamine were boiled for20 minutes. The mixture was poured into water and the precipitate formedwas filtered and crystallized from ethyl alcohol. An orange amorphusproduct having M.P. 284-5C was obtained.

(A max of absorption in ethanol: 498 nm) Example 26 5-[(1-B-acetoxyethyl)-3-ethyl-5.6-dich1orobenzimidazoline-Z-yIidene-ethylene]-3-furfuryl-2-thiooxazolidone.

Example 27 l-2-dihydro-1 -methyl-pyridin-2-ylidene )-3-furfuryl-2-thiooxazolidone 1.97 g of N-furfuryl-2-thio-oxazolidone, 2.67 g of 2-methylmercapto-pyridine-iodoethylate, 25 cc of ethyl alcohol 2.5 cc oftriethylamine were boiled for min utes. By cooling the orange solutionthus obtained, the raw dye separated out; the dye was crystallized fromethyl alcohol. Yellow needles were obtained.

(A max of absorption in ethanol: 430 nm).

Example 28 5-( 3-methyl-benzothiazoline-2-ylidene)-3-furfuryl-2-thiooxazoliclone 0.98 g of N-furfuryl-2-thio-oxazolidone, 1.61 g of 2-methylmercapto-benzothiazole-iodo-methylate, cc of ethyl alcohol, 2 ccof triethylamine were boiled for 5 minutes. The dye separatedimmediately and was crystallized from N,N-dimethyl-formamide. Yellowneedles having a M.P. 280-1C were obtained.

(A max of absorption: 405 nm).

Example 29 5 3'ethyl-5,6-dimethyl-benzoxazoline-2-ylideneethylene)-2-thio-3-furfuryloxazolidone 0.98 g of 3-furfuryl-2-thio-oxazolidone, 2.23 g of2-(wacetanilidoviny1)-5,6-dimethyl-benzothiazole-iodoethylate, 10 cc ofethyl alcohol and 1 cc of triethylamine were boiled for 30 minutes. Themixture was filtered and the product was crystallized from pyridine. Anorange amorphous product having M.P. 276-7C was obtained.

(A max of absorption in ethanol: 472 nm).

Example 30 5 3 -ethyl-benzothiazoline-2-ylidene-isobutilidene- 3tetrahydrofurfuryl-2-thio-oxazolidone H Cz O 0.4 g ofN-tetrahydrofurfuryl-2-thio-oxazolidone, 0.8 g of 2-( 2-ethylmercapto-3-butenyl )-benzothiazole-iodoethylate, 8 cc of ethylalcohol, 0.8 cc of triethylamine were boiled for 10 minutes. The mixturewas cooled and diluted with acidified water. A dark pitchy material withviolaceus reflexes separated out. It was crystallized from ethyl alcoholand red violaceus crystals having MP. l34135C were obtained.

(A max of absorption in ethanol: 502 nm).

Example 31 5-(3-ethylbenzothiazoline-Z-yIidene-isopropylidene3-furfuryl-2-thio-oxazolidone 0.4 g of N-furfuryl-2-thio-oxazolidone,0.87 g of 2-(2-ethylmercapto-propenyl)-benzothiazole-ethylparatoluenesulfonate, 8 cc ofethyl alcohol, 0.8 cc of triethylamine were boiled for 5 minutes. Thedye separated out and was crystallized from pyridine. Red violetcrystals 5 having M.P. 224-5C were obtained.

(A max of absorption in ethanol: 497 nm).

0.8 g of N-tetrahydrofurfuryl-2-thio-oxazolidone, 0.94 g of2-(2-ethyl-mercapto-propenyl)-benzothiazole ethyl-p-toluensulfonate, 8cc of ethyl alcohol, 0.8 cc of triethylamine, were boiled for 10minutes. the dye separated out and was crystallized from a mixture ofpyridine and ethyl alcohol 1:1. Red mycrocrystals of the dye having M.P.l979C were obtained. (A max of absorption in ethanol: 499 nm).

Example 33 5-(3-ethyl-benzothiazoline-2-ylidene-isobutylidene)-3-furfuryl-2-thio-oxazolidone 0.4 g of N-furfuryl-2-thio-oxazolidone, 0.8g of 2-(2- ethylmercapto-butenyl)-benzothiazole-iodoethylate, 8 cc ofethyl alcohol and 0.8 cc of triethylamine, were boiled for 5 minutes. Bystanding the dye separated out and was crystallized from ethyl alcohol.Purplish pink crystals of the dye, having M.P. l67-9C were obmined.

(A max of absorption in ethanol: 500 nm) Example 34 5-(3-ethyl-5-methyl-benzoselenazoline-Z-ylideneisobutylidene )-3-furfuryl-2-thio-oxazolidone 0.59 g of N-furfuryl-2-thio-oxazolidone, 0.93 g of 2-(2-ethylmercapto-3-butenyl)-5-methylbenzoselenazole ethyl p.toluensulfonate, 8 cc of ethyl alcohol and 0.8 cc of triethylamine wereboiled for 15 minutes. By cooling the dye separated out and wascrystallized from a large amount of ethyl alcohol. An orange amorphousproduct was obtained having M.P. l83.5-184.5C

(A max of absorption in ethanol: 507 nm) Example 35 5-(3-ethyl-5-methyl-benzoselenazoline-2-ylideneisobutylidene )-3-tetrahydrofurfuryl-2-thio-oxazolidone 0.6 g ofN-tetrahydrofurfuryl-2-thio-oxazolidone, 1.5 g of2-(2'-ethylmercapto-3-butenyl)-5- methylbenzoselenazole ethylp-toluenesulfonate, 8 cc of ethyl alcohol, 0.8 cc of triethylamine, wereboiled for 10 minutes. The mixture was precipitated with water. The dyewas separated and crystallized from ethyl alcohol. Orange crystalshaving M.P. 2l5-7C were obtained.

(A max of absorption in ethanol: 506 nm).

Example 36 5-( 3-ethyl-naphthol ,2-4,5-oxazoline-2-ylideneethylidene)-3-furfuryl-2-thiooxazolidone o s N N i JJ'HS din Zll 1.97 g ofN-furfuryl-2-thio-oxazolidone, 4.84 g of2-(wacetanilidovinyl)-B-naphthooxazole-iodo-ethylate, 40 cc of ethylalcohol and 4 cc of triethylamine, were boiled for 10 minutes. Theorange dye separated in the hot. It was filtered and crystallized frompyridine. Red orange crystals having MP. 285-6C;

(A max of absorption in ethanol: 486 nm) Example 37 5-(l-,8-acetoxyethyl-3-ethyl-5,6-dichlorobenzimidazoline-2-ylidene-ethylidene l -furfuryl-3-propyl-Z-thio-hydantoin thiodantoin, 4.42 g ofl-B-acetoxyethyl-2-methyl-5,6- dichloro-benzimidazoleiodo-ethylate, 30cc of N,N-dimethylformamide and 3 cc of triethylamine were reacted for30 minutes at 150C. The hot mixture was poured into hot water thendecanted and the washing was repeated several times. The product wasdissolved in boiling ethyl alcohol and was allowed to stand. Theobtained dye weighed 2.3 g and had a M.P. l73-5C (Purplish pinkcrystals).

(A max of absorption in ethanol: 522 nm) Centesimal analysis Example 385-( 3-ethyl-5-methoxy-benzoselenazoline-2-ylideneethylidene)-l-furfuryl-3-('y-dimethylaminopropyl)-2- thiohydantoin G=CH-CH=C-NCHa-C6 N 0=b\ s 011-- H 2H5 N CH3 (iHicmcmN 5.62 g ofl-(furfuryl)-3(y-dimethylaminopropyl)- 2thiohydant0in, 5.06 g of 2(w-aldehydomethylene)-3- ethyl--methoxy-benzoselenazolidene, cc ofpyridine, 2 cc of acetic anhydride were boiled for 15 minutes. Bystanding overnight the dye separated out; it was filtered andcrystallized from pyridine. Purplish red crystal of dye having M.P.194-5C were obtained. (A max of absorption in ethanol: 528 nm)Centesimal analysis Example 39 5-(3-methyl-5-bromo-benzoxazoline-Z-ylideneethylidene l-furfuryl-3-propyl-2-thio-hydantoin 2.39 g ofl-furfuryl-3-propyl-2-tiohydantoin, 4.83 g of2-(w-acetanilidevinyl)-5-bromo-benzoxazole-iodomethylate, 30 cc of ethylalcohol and 3 cc of triethylamine were boiled for 10 minutes. The dyeseparated by cooling and was crystallized from pyridine. Red orangecrystals having M.P. 254-5C were obtained. (A max of absorption inethanol: 479 nm) Example 40 5-(3-ethyl-5-acetylamino-benzoxazoline-Z-ylideneethylidene l-furfuryl-3-propyl-2-thiohydantoin 2.39 g of1-furfuryl-3-propyl-2-thiohydantoin, 4.1 g ofZ-(w-acetanilidovinyl)-3-ethyl-5-acetylamino-benzoxazole-iodo-ethylate,20 cc of butyl alcohol and 4 cc of piperidine were boiled 20 minutes.The dye separated by standing was filtered and crystallized from ethylalcohol.

()t max of absorption in ethanol: 488 nm) Example 41 5-(3,5-dimethyl-benzoxazoline-2-ylidene-ethylidene)- 1-furfuryl-3-propyl-2-thyo-hydantoin 2.39 g ofl-furfuryl-3-propyl-2-thiohydantoin, 4.3 of2-(w-acetanilidovinyl)-benzoxazole-iodo-ethylate, 60 25 cc of butylalcohol, 5 cc of piperidine, were boiled for minutes. The dye separatedby standing was crystallized from pyridine. Ocre crystals having M.P.l86.5l87C were obtained.

(A max of absorption in ethanol: 481 nm).

Example 43 5 3-methyl-5-phenyl-benzoxazoline-2-ylideneethylidene)-1-furfuryl-3-propyl-2-thiohydantoin5 /c=oH cH=Z--1I crno Q \N 0 s OH H N CH3 (I:

ZCI' QCHS 45 2.39 g of l-furfuryl-3-propyl-2-thiohydantoin, 4.96 g ofZ-(w-acetanilidovinyl)-5-phenyl-benzoxazole-iodomethylate, 80 cc ofbutyl alcohol, 8 cc of piperidine were boiled for 1 hour. The dyeseparated by cooling and was crystallized from piperidine. A light brownamorphous product having M.P. 2624 C was obtained. (A max absorption inethanol: 485 nm) Example 44 5 3-ethyl-5,7-dimethyl-benzoxazoline-Z-ylideneethylidene)- l-furfuryl-3-propyl-2-thiohydantoin O /OCH CH3 c=oH-orr=o N om o l \N/ CH1H 24 2.39 g of l-furfuryl-3-propyl-2-thiohydantoin, 4.62 g ofZ-(A-acetanilidovinyl)-5,7-dimethylbenzoxazole-iodoethylate, 20 cc ofbutyl alcohol and 4 cc of piperidine were boiled for 20 minutes. The dyeseparated by cooling and was crystallized from pyridine. Red orangecrystals of the dye having M.P. 197-9C were obtained. (A max ofabsorption in ethanol: 492 nm) Example 45 5-(3-ethyl-benzoxazoline-Z-yIidene-ethylidene lfurfuryl-3-carboxymethyl-2-thiohydantoin C=CHCH=CNOHz-C \N o: s 011- Hon N 0.508 g of 1-furfuryl-3-carboxymethyl-2- thiohydantoin, 0.868 g of2-(w-acetanilidovinyl)- benzoxazole-iodo-ethylate, 7 cc of pyridine and1 cc of triethylamine were boiled for 10 minutes. After cooling waterwas added and the mixture was acidified with acetic acid. The dyeseparated out and was crystallized from pyridine acidified with aceticacid. Dark orange crystals having M.P. 2634C were obtained.

(A max of absorption in ethanol: 479 nm).

Example 46 53-ethyl-5,6-dimethyl-benzoxazoline-Z-ylideneethylidene)-1-furfuryl-3-carboxymethyl-2-thiohydantoin thiohydantoin, 0.892 g of Z-(A-acetanilidovinyl)-5,6-dimethyl-benzoxazole-iodo-ethylate, 7 cc of pyridine and 1 cc oftrimethylamine were boiled for 10 minutes. After cooling water was addedand the mixture was slightly acidified with acetic acid. Purple pinkcrystals of the dye having M.P. 258260C. were obtained (A max ofabsorption in ethanol: 490 nm).

Example 47 5-(3-ethyl-5-phenyl-benzoxazoline-2-ylideneethylidene-1-furfuryl-3(y-dimethylamino-propyl)-2-thiohydantoin 1.4 g of 1-furfuryl-3-('y-dimethylaminopropyl)-2-thiohydantoin, 2.55 g of 2-(w-acetanilidovinyl)-5-phenyl-benzoxazole-iodoethylate, cc of ethyl alcohol and 1.5 cc ofpiperidine were boiled for minutes. The dye separated out and wascrystallized from pyri- 5 dine. Red orange crystals of dye having M.P.2257C were obtained. (A max of absorption in ethanol: 490 nm) Example 485-(3-ethyl-5-chloro-benzoxazoline-2-ylideneethylidene)-1-furfuryl-3(y-dimethylaminopropyl)-2-thiohydantoin 1.4 g of l-furfuryl-3-('y-dimethylaminopropyl)-2-thiohydantoin, 2.34 g of 2-(w-acetanilidovinyl)-5-chloro-benzoxazole-iodoethylate, 4 cc of pyridine and 0.5 cc oftriethylamine were boiled by 10 minutes. The dye separated by coolingand was crystallized from pyridine. An orange amorphous product havingM.P. 2l02C was obtained.

(A max of absorption in ethanol: 480 nm).

The compound was prepared analogously to Example 48 using the S-methylderivative of the benzoxazole instead of the 5-chloro derivative. Redorange crystals. M.P. 192-4C.

(A max of absorption in ethanol: 488 nm) Example 50 5 5 5-(3-ethyl-5-acetylamino-benzoxazoline-Z-ylideneethylidene)-1-furfuryl-S-(y-dimethylaminopropyl)-2-thiohydantoin 011.10 ONIlmn- -N (Illa The compound was preparedanalogously to Example 48 using the 5-acetylamino derivative of thebenzoxazole instead of the 5-chloro derivative. Violet crystals. M.P.l5l-2C. (A max of absorption in ethanol: 494 nm) Example 5 1 5-( 3-ethyl5-metoxy-benzoxazoline-2-ylideneethylidene l-furfuryl-3-(y-dimethylaminopropyl )-2- thiohydantoin The compound wasprepared analogously to Example 48, using the 5-methoxy derivative ofthe benzoxazole instead of the 5-chloro derivative. Orange amorphousproduct. M.P. 227-8C.

(y max of absorption in ethanol: 491 nm) Example 52 5-(3-ethyl-5,6-dimethyl-benzoxazoline-2-ylideneethylidene l-furfuryl-3-(-y-dimethylaminopropyl)-2- thioydantoin The compound wasprepared analogously to Example 48, using the 5,6-dimethyl derivativeinstead of the 5- chloro derivative.

(A max of absorption in ethanol: 493 nm) Example 53 5-( 3-ethyl-5,7-dimethyl-benzoxazoline-2-ylideneethylidene)-1-furfuryl-3-(-y-dimethylaminopropyl)-2-thioydantoin The compound was prepared according to what reported forExample 48, using the 5,7-dimethyl derivative of the benzoxazole insteadof the -chloro derivative. M.P. 22l-3C. Red brick amorphous product. (Amax of absorption in ethanol: 489 nm) Example 54 5-(3-ethyl-benzoxazoline-2-ylidene-ethylidene lmethyl-3-tetrahydrofurfuryl-2-thiohydantoin thiohydantoin, 1.02 g of2-(w-acetanilidovinyl-benzoxazole-iodo-ethylate, 7 cc of ethyl alcoholand 1 cc of triethylamine were boiled for minutes. The dye separated bycooling and was crystallized from pyridine. Red orange crystals of dye,having M.P. 215-7C were obtained.

(A max of absorption in ethanol: 480 nm) Example 55 5-(3-ethyl-5-phenyl-benzoxazoline-Z-ylideneethylidene l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin The compound was obtainedanalogously to Example 54, using the S-phenyl derivative of thebenzoxazole. M.P. 218-9C. Purple pink crystals.

()t max of absorption in ethanol: 486 nm) Example 5 6 5(3-ethyl-5-methyl-benzoxazoline-2-ylideneethylidene l-methyl-3-tetrahydrofurfuryl-2- thiohydantoin The compound was obtainedanalogously to Example 54, using the S-methyl derivative of thebenzoxazole. The product was orange and amorphous with M.P. 240-lC.

(A max of absorption in ethanol: 484 nm) Example 57 5-(3-ethyl-5-chloro-benzoxazoline-Z-ylideneethylidene)-1-methyl-3-tetrahydrofurfuryl-2-thiohydantoin din-mi,

The compound was obtained analogously to Example 54 using the 5-chloroderivative of the benzoxazole. The product was orange and amorphous,with M.P. 250.5251.5C.

(A max of absorption in ethanol: 478 nm) Example 58 5-(3-ethyl-5,7-dimethyl-benzoxazoline-2-ylideneethylidene l-methyl-3-tetrahydrofurfuryl-2- thiohydantoin The compound was preparedanalogously to Example 54 using the 5,7-dimethyl derivative of thebenzoxazole; the product was in orange crystals with M.P. 239.5-240C.

(A max of absorption in ethanol: 492 nm) Example 59 5-(3-ethyl-5-acetylamino-benzoxazoline-Z-ylideneethylidene )-l-methyl-3-tetrahydrofurfuryl-2- thiohydantoin HaCC ONH 1r 2 \O JEEP-dimThe compound was prepared analogously to Example 54, using theS-acetylamino derivative of the benzoxazole, in red orange microcrystalshaving M.P. 280-lC.

()t max of absorption in ethanol: 487 nm).

Example 60 5-(3-ethyl-5,6-dimethyl-benzoxazoline-2-ylideneethylidene)-1-methyl-3tetrahydrofurfuryl-2-thiohydantoin 926 l C was obtained. (A max of absorption in ethanol: 495nm).

Example 61 5-(3-ethyl-naphtho-2',l -4,S-oxazoline-2-ylideneethylidene l-methyl-3-tetrahydrofurfuryl-2- thiohydantoin \N O: S

( lgHa 1? The compound was prepared analogously to Example 54, using thenaphto-2.l '-4,5-oxazole derivative. M.P. 270"-7"272(. Dark redcrystals.

(A max of absorption in ethanol: 496 nm).

Example 62 5-(3-ethyl-naphtho-2'. l '-4.5-oxazoline-2-ylideneethylidenel -furluryl-3-('y-dimethylaminopropyl )-2- thiohydantoin Ulla 1.4 g of1-furfuryl-3-(y-dimethylaminopropyl)-2- thiohydantoin, 2.42 g of2-(w-acetanilidovinyl)- napththo-2',l '-4,5-oxazole-iodo-ethylate, 8 ccof ethyl alcohol, 2 cc of piperidine were boiled for 20 minutes. Waterwas added to the reaction mixture and the latter was allowed to stand.The dye separated out was filtcred and crystallized from pyridine. Redcrystals of the dye having a MP. l7C were obtained. (A max of absorptionin ethanol: 505 nm).

Example 63 5-( 3-ethyl-naphtho-l ,2-4,5 oxazoline-Z-ylideneethylidene l-furfuryl-3-propyl2-thiohydantoin I at.

0.239 g of l-furfuryl-3-propyl-2-thiohydantoin, 0.48 g of2-(w-acetanilidovinyl)-naphtho-1,2'-4,5-oxazoleiodo-ethylate, 4 cc ofethyl alcohol, 0.4 cc of triethylamine were boiled for 1 minute. The dyeseparated immediately and was crystallized from pyridine. An orangeamorphous product having MP. 2424C was obtained.

(A max of absorption in ethanol: 504 nm).

Example 64 5 3-ethyl-naphtho.-l ,2 -4,5-oxazoline-2-ylideneethylidene l-methyl-3-tetrahydrofurfuryl-2- thiohydantoin l lltl llr The compoundwas prepared analogously to Example 54 using the naphtho-l',2-4,5-oxazole. (A max of absorption in ethanol: 502 nm).

Example 65 -(3-ethyl-naphtho-l ,2-4,5-oxazoline-2-ylideneethylidene l-furfuryl-3-('y-dimethylaminopropyl )-2- thiohydantoinnaphtho-l,2-4,5-oxazoleiodo-ethylate, 5 cc of pyridine, 1 cc oftriethylamine were boiled 20 minutes. A crystalline solid separated outand was crystallized from pyridine.

(A max of absorption in ethanol: 504 nm) Example 66 5-(B-methyI-naphtho-l ,2-4,5-oxazoline-2-ylideneethylidene)-1-furfuryl-3-carboxymethyl-2- thiohydantoin thiohydantoin, 0.968 g of2-(w-acetanilidovinyl)- naphtho-l,2-4,S-oxazole-iodoethylate, 7 cc ofpyridine and 1 cc of triethylamine were boiled for 10 minutes. Byaddition of water and of acetic acid the dye separated out and waspurified by hot-dissolving in pyridine and acidification with aceticacid. The dye obtained presented a M.P. 25961C.

(A max of absorption in ethanol: 500 nm).

. Example 67 5-(3-methylnaphtho-l ,2'-4,5-oxazoline-2-ylidene- 1.14 g ofl-(tetrahydrofurfuryl)-3-ethyl-2- thiohydantoin, 2.35 g of2-(w-aldehydomethylene)- naphtho-l',2-4,5-oxazoleiodo-ethylate. 5 cc ofethyl alcohol and 0.5 cc of triethylamine were boiled for 10 minutes.

The separated dye was crystallized from ethyl alcohol. ()t max ofabsorption in ethanol: 504 nm).

Example 68 5-( 3-methyl-naphtho-4,5-oxazoline-2-ylideneethylidene lfurfuryl )-3-propyl-2-thiohydantoin 0.239 g ofl-(furfuryl)-3-propyl-2-thiohydantoin, 0.47 g of2-(w-acetanilidovinyl)'-naphtho-4,5-oxazole-i0doethylate, 3,5 cc ofbutyl alcohol, 0.5 cc of piperidine were boiled for 15 minutes. The dyeseparated out and was crystallized from pyridine. The dye dried in theoven has M.P. 2535C. Dark red crystals.

(A max of absorption in ethanol: 486 nm) Example 69 5-(3-ethyl-naphtho-4,5-oxazoline-2-ylideneethylidene l-methyl-3-tetrahydrofurfuryl-2- thiohydantoin (I: N 2H5 CH: 5 014. 1H1CH7 0. 5 3 g of 1-methyl-3 -tetrahydrofurfuryl-2- thiohydantoin, 1.17 gof Z-(w-acetanilidovinyD- naphtho-4,5-oxazole-iodo-ethylate, 7 cc ofethyl alcohol and 1 cc of triethylamine were boiled for 4 minutes. Theseparated dye, cristallized from pyridine in pink microcrystals. M.P.2768C.

(A max of absorption in ethanol: 487 nm) Example 70 5-(3-methylnaphtho-4,5-oxazoline-2-ylideneethylidene )-l-furfuryl-3-(y-dimethylaminopropyl)-2- thiohydantoin CH II ills

2. Photographic element having a photosensitive layer containing thesilver halide emulsion according to claim
 1. 3. The emulsion of claim 1wherein the alkyl group R is a hydroxyalkyl, sulfoalkyl, carboxyalkyl oralkaryl.
 4. The emulsion of claim 1 wherein R represents benzyl orparacarboxyphenylmethyl.
 5. The photographic emulsion of claim 1 whereinQ completes a thiazolone, rhodanine, oxazolone, pseudo-hydantoin,hydantoin, thiohydantoin, imidazolone, oxindole, 3,4-dihydroquinolone,pyrazolone, 3,4-dihydroquinoxazolone, 2,4,6-triketo-hexahydropyrimidine,or 1,4-morpholine-3-one nucleus.